Process for the development of silver halide light-sensitive material

ABSTRACT

M IS A POSITIVE INTEGER OF AT LEAST 2, N IS O or a positive integer, p is 1 or 2, X is an anion, and Z is an organic chemical structure necessary for completing a heterocyclic ring together with N , is disclosed. The scope of the present invention also extends to the developed product formed, the developing compounds employed and their process of preparation.   WHEREIN R is a hydrogen atom, an alkyl group, an alkylphenyl group or -(CH2)m-OR&#39;&#39;, R&#39;&#39; is a hydrogen atom, an alkyl group or   A process for the development of silver halide photographic materials which comprises developing photographic materials in the presence of a compound of the formula:

United States Patent Yoneyama et al.

[451 Nov. 13, 1973 PROCESS FOR THE DEVELOPMENT OF SILVER HALIDE LIGHT-SENSITIVE MATERIAL [75] Inventors: Masakazu Yoneyama; Isao Shimamura; Haruhiko Iwano; Reiichi Ohi, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan 22 Filed: Oct. 9, 1970 211 Appl. No.: 79,627

Primary ExaminerNorman G. Torchin Assistant Examiner-John L. Goodrow Attorney-Sughrue, Rothwell, Mion, Zinn and Macpeak [57] ABSTRACT A process for the development of silver halide photographic materials which comprises developing photographic materials in the presence of a compound of the formula:

wherein R is a hydrogen atom, an alkyl group, an alkylphenyl group or (CI-I ),,,OR, R is a hydrogen atom, an alkyl group or m is a positive integer of at least 2, n is O or a positive integer, p is l or 2, X is an anion, and Z is an organic chemical structure necessary for completing a heterocyclic ring together with N, is disclosed. The scope of the present invention also extends to the developed product formed, the developing compounds employed and their process of preparation.

14 Claims, No Drawings PROCESS FOR THE DEVELOPMENT OF SILVER HALIDE LIGHT-SENSITIVE MATERIAL BACKGROUND OF THE INVENTION This invention relates to a process for the development of silver halide light-sensitive materials.

In the development of silver halide light-sensitive materials, there is a demand for higher rater of development and higher sensitivity. Hitherto it has been known to add an amine compound as a development accelerator in a developer in order to attain this effect. However, many of the amine compounds, in general, have various drawbacks such as a bad odor, volatility too high to maintain constant cocentration in the developing solution, and potent toxicity. In addition, they usually are not effective in increasing the sensitivity, though they do accelerate the rate of development. They also are undesirable from the standpoint that they increase fog, generate scum or stain during development, and degradate grain granularity of developed silver grains. Besides amine compounds, quaternary salt compounds are also known to possess an accelerating effect as disclosed by T. H. James in Phot. Sci. Tech., vol. 19B, pp. 35 (1953).

DESCRIPTION OF THE PRIOR ART SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide an improvement in the development process by using a development accelerator which increases the rate of development and effective sensitivity without any increase in fog or any degradation of granularity of developed silver grains.

This object is attained by using a quarternary salt compound having a hydroxyl group in the B-position to N as represented by the following general formula,

wherein R is a hydrogen atom, an alkyl group, an alkylphenyl group or -(CI-I -OR', R being a hydrogen atom, an alkyl group or m being an integer of at least 2, n being or a positive integer, p being 1 or 2, X being an anion, and Z being an organic chemical structure for completing the heterocyclic ring together with N such as pyridinium, imidazolium or quinolinium ring.

Com und 1.

-cH,cHcH,0cn:-c1

Com und 2.

-CH;CHCHrOCzH-Cl' Compound 3.

- ICH CHCH OC H -Cl' Compound 4. i

I-CH, CHCH30C4HQ-C1 Compound 5.

CH3CHCH1OC5H13 Cl C 6H Compound 6.

cn,oncn,oouum 01- Compound 7. CIH3 HN +N-CH: CHCHaO CHa-CP Compound 8. CH

nN N-cmcucmoozmci- Compound 9. CH3

HN +NCHCHCH OC3H -C1' Compound 10. CH;

HN +NCH1 CHCHQO cHflCl H (11) (IIHQ HN +N-CH CHCH O Cd-In- Cl These compounds may be prepared in a straightforward manner as shown below. Synthesis of Compound 2 To 5 moles of ethyl alcohol there is added dropwise 1 mole of epichlorohydrin with stirring, in the presence of stannic chloride as a catalyst. After the addition of epichlorohydrin, the mixture is refluxed for about 2 hours, then cooled to room temperature. A small amount of water is added to the mixture to decompose the catalyst. The mixture is then dried, filtered and distilled, and then refluxed for 8 hours in a large excess of pyridine. The compound 2 is obtained after the elimination of the excess pyridine by distillation. Synthesis of Compound 8 l Mole of l-ethoxy-3-chloropropanol-2 synthesized in the manner as in the above example and 1 mole of Z-methylimidazole are dissolved in dioxane and the resulting solution is heated for about hours. The reaction mixture is then washed with ethyl acetate to obtain the Compound 8.

Synthesis of Compound l2 3 Moles of ethylene oxide is added to 1 mole of nonylphenol in a conventional manner. The adduct is then reacted with 1 mole of epichlorohydrin using stannic chloride as a catalyst and then heated in a large excess of water pyridine mixture. The reaction mixture is washed with petroleum ether to obtain the Compound 12.

Synthesis of Compound A few drops of stannic chloride is added to 1 mole of l,4-butanediol and heated at 85 to 95C. Then 2 moles of epichlorohydrin is added dropwise thereto with stirring. The stirring is continued for 24 hours. Unreacted epichlorohydrin is removed from the reaction mixture under reduced pressure, and 150 cc of ether is added to the residue. Then 142 parts of 50% aqueous caustic soda is added dropwise with vigorous stirring and cooling by ice. The stirring is continued until the exothermic reaction ceases, and the ether layer is separated. The reaction mixture is extracted twice with each 100 cc of ether. The ether parts are collected, dried by anhydrous sodium sulfate and, after removal of ether by distillation, refined to obtain a monoglycidyl ether of a boiling point of l14-5C/2.5 mm Hg and a diglycidyl ether of a boiling point of l23-4C/2.5 mm Hg. One mole of the diglycidyl ether is dissolved in 600 cc of dioxane and gaseous hydrogen chloride is then introduced into the solution with stirring and cooling until hydrogen chloride becomes excessive. The solution is then allowed to stand overnight. The solution is heated on a steam bath for about 1 hour, and nitrogen gas is then introduced to eliminate any excess of hydrogen chloride. After elimination of dioxane under reduced pressure, the reaction product is refluxed in an excess of hydrous pyridine for 14 hours. During the reflux, the reaction mixture gradually separated to two phases. After removal of the lower layer, pyridine was elirninated from the upper layer. The residue of upper layer is dissolved in a small amount of water and then washed with ether to obtain the Compound 15.

The compounds l,3,4,5 and 6 are synthesized by using methanol, propanol, butanol, hexanol and tetradecyl alcohol respectively in the manner as prescribed in the synthesis of the Compound 2.

The compounds 7,9,l0 and 1 l are synthesized in the manner as prescribed in the synthesis of the Compound 8 by use of methanol, propanol, butanol and hexanol, respectively.

The Compound 13 is synthesized in the similar manner as in the synthesis of the Compound 18 by use of the monoglycidyl ether.

The Compounds 14 and 16 are synthesized in the same manner as in the synthesis of the Compound 15.

The compounds of the present invention are applicable to the ordinary silver halide photosensitive materials, such as, e.g., black and white positive materials of relatively low sensitivity, black and white negative materials of relatively high sensitivity, X-ray materials and color materials.

Although the known amine compounds and quaternary salt compounds have development accelerating effects and sensitivity increasing effects, they have a drawback of increasing fog. The compounds of the present invention are free from the drawback of increasing fog and moreover considerably accelerate the rate of development and increase the sensitivity.

Furthermore, they do not lower the sharpness of the developed image and deteriorate the granularity of developed silver grains in contrast to known development accelerators.

While the exact reason for the low fog level and the high sensitizing effect of the compounds of the present invention is uncertain at present, it is believed to be attributable to the distinctive structure of the compound of the present invention.

The developing solution in which the compounds of the present invention are used are the ordinary developing solutions which contain at least one of the following compounds, and their known derivatives, as the developing agents: hydroquinone, l-phenyl-3 pyrazolidone, N-methyl-p-aminophenol, N,N-diethylp-phenylenediamine. The developing solutions may contain, in addition to the developing agent, preservatives, such as sodium sulfite, ascorbic acid or hydroxylamine, pH adjusting or bufiering agent, such as sodium sulfate, boric acid, borax, sodium hydroxide, sodium carbonate or trisodium phosphate, development retarders, such as potassium bromide or potassium iodide, or anti-fogging agents, such as 6- nitrobenzimidazole, benzotriazole or 1 mercaptotetrazole. Occasionally, formaldehyde, glutaraldehyde or like aldehydes, or triethylene glycol, hexylene glycol or like organic solvents are added to the developing solution. The compound of the present invention may be used in combination with amines andfor polyethylene glycols which have been known as development accelerators in the past.

DETAILED DESCRIPTION OF THE INVENTION The compounds of the present invention may be effectively incorporated in a developing solution, in a bath preceding the development step andfor in a silver halide emulsion. Satisfactory results are obtainable, in most cases, by use of one of the compounds of the present invention, though, in certain cases, an increased effect may be obtained by a combined use of two or more of the compounds of the present invention. When the compounds of the present invention are incorporated in a developing solution, the compound of the present invention is usually used in a concentration of from 0.01 to 20 parts/l and preferably 0.1 to 10 parts/l, depending upon composition of the solution. In cases of incorporating said compounds in a silver halide emulsion, it is preferable to incorporate these compounds in an amount of from 0.01 to 20 parts per mole of silver halide, depending on the composition of the emulsion and/or the method of sensitizing applied to the emulsion. In this instance, although the compound may be added to the emulsion in any stage of the preparation thereof, best results are obtained when it is added to the emulsion between chemical sensitization and coating. The compound may be incorporated in a contiguous layer such as a protective layer instead of incorporating directly in the emulsion layer. In this case, the compound in the contiguous layer migrates immediately or during the later processes including development into the emulsion layer.

The silver halide emulsion used in the practice of the present invention includes those containing silver chloride, silver bromide, silver chlorobromide, silver iodide, silver iodobromide or silver chloro-iodobromide. The emulsion may be chemically sensitized by means of an unstable sulfur compound and/or a gold compound. The emulsion may be spectrally sensitized by means of, e.g., a cyanine dye or merocyanine dye. The emulsion may be stabilized by a heterocyclic compound such as, e.g., 4-hydroxy-6-methyl-1,3,3a, 7- tetrazaindene or l-phenyl-5-mercaptotetrazole. The emulsion may be hardened by known hardeners such as formaldehyde or mucochloric acid or may contain a surface active agent as a coating aid. In addition, the emulsion may contain a color coupler capable of reacting with an oxidized product of an aromatic primary amine developing agent to form a color image.

A better understanding of the present invention will be attained from the following examples, which are merely illustrative and not limitative of the present invention. All parts are by weight unless otherwise stated.

EXAMPLE 1 A commercially available fine grain positive cine film comprising a fine grain silver chloroiodobromidegelatin emulsion was developed at 20C in a developing solution of the following composition.

Water 800 parts (by volume) N-methyl-p-aminophenol sulfate 1.7 parts Sodium sulfite 50 parts Hydroquinone 4.4 parts Borax parts Potassium bromide .5 parts Water added to the total volume of 1 liter The above developing solution ordinarily required a developing time of 8 minutes.

The developing time could be shortened by addition of a compound of the present invention (Compoundto the developing solution as indicated in the following Table I. On the other hand, another test strip which was developed for 8 minutes in the presence of the compounds of the present invention showed an increase in sensitivity as indicated also in the Table 1. For comparison, the photographic characteristics in the case where a known quaternary ammonium salt compound-l7 was added were also indicated in the Table l.

EXAMPLE 2 A commercial high speed film comprising a spectrally sensitized silver iodobromide-gelatin emulsion was developed at C in a developing solution of the following composition.

Water 800 parts (by volume) l-phenyl-3-pyrazolidone 0.2 parts Sodium sulfite 100 parts l-lydroquinone 5 parts 10 Borax 2 parts Boric acid 1 part Potassium bromide 1 part Water added to a total volume of 1 liter 15 The developing solution ordinarily required a developing time of 8 minutes, but the time could be shortened by addition of a compound of the present invention (Compound-l5) to the solution as indicated by the following Table-2.

In the Table-2 there were also indicated the photographic characteristics in the case where a known compound-l 8 was used for comparison.

TABLE 2 Amount Developing time for 8 min. Developadded ing time Compound (g./l.) RS. Fog 7 (min.)

Control 0 100 O. 24 0. 7O 8 Compound 15... 1 185 0. 26 0. )8 5% Compound 18* 1 130 0. 38 0. 82 7 1 Necessary for R.S. of 100.

*Compound 18:

"\'N(CH2):4N: -2Cli The above results indicate that the compound of the present invention results in a higher sensitivity with lower fog than the known compound.

EXAMPLE 3 side the scope of the compound of the present invention were also indicated in the Table-3.

Table 3 Compound Amount Relative Fog 7 Added(mol/l) sensitivity Control 0 0.18 0.68 Compound-l5 5 X 10' 0.18 1.00 Compound-19* 5 X 10 H0 0.31 1.12

*Compound- I 9 As evident from the above results, the addition of the compound of the present invention results in a high sensitivity with a small increase in fog compared with the control. Compared with the results obtained by addition of the Compound-19, Compound-15 of the present invention exhibited less fog and proved superior in sensitivity and gamma.

A commercially available fine grain positive cine film comprising a fine grain silver chloroiodobromidegelatin emulsion was developed using the same developing solution as in Example 1 at 20C for 8 minutes. Separately, other pieces of the film were developed in the same manner using the same solution except that a compound of the present invention (Compound 1 to 5) or a Compound 20 which was outside the scope of the present invention had been added for comparison. The results obtained were summarized in the Table-4.

Table-4 Compound Amounts added Relative Fog 7 (mol/l) sensitivity Control 100 0.04 1.70 Compound-1 1 X 10 125 0.06 1.76 Compound-2 1 X 10 140 0.05 1.92 Compound-3 1 X 10 130 0.04 1.78 Compound-4 I X 10 135 0.05 1.85 Compound-5 l X 140 0.06 1.80 Compound-20 1 X 10" 102 0.38 1.65

Compound-20 EXAMPLE 5 A microfilm prepared by applying a fine grain silver chlorobromoiodide-gelatin emulsion to a support was developed at 20C in a developing solution of the formulation as follows:

Water 800 parts (by volume) N-methyl-p-aminophenol sulfate 1 part Sodium sulfite 75 parts l-lydroquinone 9 parts Sodium carbonate monohydrate 29 parts Potassium bromide 6 parts Water is added to a total volume of 1 liter Although the developing solution ordinarily required a developing time of 4 minutes, the developing time could be shortened by addition thereto of a compound of the present invention (Compound 7 to 11) as indicated by the Table-5, and a high sensitivity was obtainable by conducting the development for 4 minutes in the presence of the compound of the present invention as indicated by the Table-5.

Table-5 Time for obtaining a Relative Development for Amounts 4 min.

An aqueous solution of the Compound 12 or 15 of the present invention was added to a silver iodobromide-gelatin emulsion containing 3.0 mol% of silver iodide (1g per kg-cm.) and coated on a film support and dried. The test films thus obtained were developed at 20C for 8 minutes in the same developing solution as in Example 1. The photographic characteristics obtained were indicated in the Table-6.

Table-6 Compound Amounts Added R.S. Fog -y (g/mol silver halide) Control 0 100 0.07 0.82 Compound 12 1 145 0,08 0.94 Compound 15 l 120 0.10 0.87

Although the present invention has been adequately described in the specification and examples, it is readily apparent that numerous modifications and changes may be made without departing from the intended scope thereof.

What is claimed is:

1. A process for the development of silver halide photographic materials which comprises developing said photographic materials in the presence of a compound which increases the rate of development and effective sensitivity without increasing fog, said compound being represented by the formula:

wherein R is a hydrogen atom, an alkyl group, an alkylphenyl group or -(CH -OR, R is a hydrogen atom, an alkyl group or m is a positive integer of at least 2, n is 0 or a positive integer, with the proviso that when R is a hydrogen atom, n is a positive integer, p is 1 or 2, X is an anion, and Z is an organic chemical structure necessary for completing a heterocyclic ring together with N selected from the group consisting of pyridinium, imidazolium and quinolinium.

2. The process of claim 1 wherein n is an integer of 0 to 3, and m is an integer of 2 to 6.

3. The process of claim I wherein said developing compound is incorporated into a developing solution.

4. The process as claimed in claim 3 wherein said developing solution contains at least one member selected from the group consisting of hydroquinone, l-phenyl-3 -pyrazolidone, N-methyl-p-aminophenol and N,N-diethyl p-phenylenediamine.

5. The process of claim 1 wherein said compound is:

6. The process of claim 1 wherein said compound is:

{ N 4311201101110 tcnnrocrncnomiv 201- 7. The process of claim 1 wherein said compound is:

a V H 8. The process of claim 1 wherein the developing compound is incorporated into a silver halide emulsion.

9. The process of claim 3 wherein the concentration of the developing compound ranges from 0.01 to 20 parts per liter of said developing solution.

10. The process of claim 8 wherein the concentration of developing compound ranges from 0.01 to 20 parts/- mole of silver in said emulsion.

11. The process of claim 1 wherein more than one of said developing compounds is present during development.

12. The developed silver halide photographic material produced by the process of claim 1.

13. The process of claim 8 wherein said developing compound is added to said emulsion after chemical sensitization thereof but prior to coating thereof onto the support of the photographic material.

14. The process of claim 1 wherein said developing compound is incorporated into a layer adjacent to the silver halide emulsion layer in said silver halide photo- 0 graphic material. 

2. The process of claim 1 wherein n is an integer of 0 to 3, and m is an integer of 2 to
 6. 3. The process of claim 1 wherein said developing compound is incorporated into a developing solution.
 4. The process as claimed in claim 3 wherein said developing solution contains at least one member selected from the group consisting of hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-p-aminophenol and N,N-diethyl-p-phenylenediamine.
 5. The process of claim 1 wherein said compound is:
 6. The process of claim 1 wherein said compound is:
 7. The process of claim 1 wherein said compound is:
 8. The process of claim 1 wherein the developing compound is incorporated into a silver halide emulsion.
 9. The process of claim 3 wherein the concentration of the developing compound ranges from 0.01 to 20 parts per liter of said developing solution.
 10. The process of claim 8 wherein the concentration of developing compound ranges from 0.01 to 20 parts/mole of silver in said emulsion.
 11. The process of claim 1 wherein more than one of said developing compounds is present during development.
 12. The developed silver halide photographic material produced by the process of claim
 1. 13. The process of claim 8 wherein said developing compound is added to said emulsion after chemical sensitization thereof but prior to coating thereof onto the support of the photographic material.
 14. The process of claim 1 wherein said developing compound is incorporated into a layer adjacent to the silver halide emulsion layer in said silver halide photographic material. 